CN101200604A - Tin-doped (IV) sulfide lanthanum pigment and preparation method thereof - Google Patents
Tin-doped (IV) sulfide lanthanum pigment and preparation method thereof Download PDFInfo
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- CN101200604A CN101200604A CNA2007100559345A CN200710055934A CN101200604A CN 101200604 A CN101200604 A CN 101200604A CN A2007100559345 A CNA2007100559345 A CN A2007100559345A CN 200710055934 A CN200710055934 A CN 200710055934A CN 101200604 A CN101200604 A CN 101200604A
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Abstract
The invention relates to sn-doped (IV) lanthanum sulfide pigment and a preparation method thereof. The pigment chemical formula is SnxLa<2-x>S<3+x/2>, wherein, x is less than or equal to 0.5 and more than or equal to 0, and the color can gradually transit from yellow to orange and red. The raw materials of tin dioxide and rare earth lanthanum oxide (or lanthanum carbonate) are uniformly mixed and are put in a reaction furnace then. The inert gas of nitrogen or argon and sulfur source gas are input. Through a certain period of high temperature reaction, the sn-doped rare earth lanthanum sulfide pigment is obtained after being cooled. Through regulating the doping amount of tin, a series of nontoxic pigments continuously changing from yellow to red can be obtained. The invention can be widely applied to coloring the building materials of plastics, paints, coatings, rubbers, leather, ceramics, inks, paper, cosmetics, cement, etc.
Description
Technical field
The present invention relates to a kind of rare earth lanthanum sulfide that can be used as yellow extremely red colour system pigment doping metals tin and preparation method thereof.
Technical background
Pigment can be divided into organic and mineral dye, because it is good that mineral dye has covering power, thermal stability is good, lovely luster and dispersion force are good etc., and advantage has been widely used in many industrial circles at present, particularly aspect plastics, paint, coating, rubber, leather, pottery, printing ink, paper, makeup etc. painted.The inorganic coloring pigment of widespread use at present, for example cadmium red, cadmium yellow, chrome green because they wherein contain more and more be subjected to strict restriction in addition in many countries through the disabled metal (particularly cadmium, lead, chromium and cobalt) of legislation.And these metals are considered to have usually than high toxicity.Determine " RoHS " instruction that came into effect on July 1st, 2006 to limit in six kinds of hazardous and noxious substances using as European Union, cadmium is listed.This instruction, it is 0.02mg/L that the limit standard of cadmium in the daily necessities is revised by original 0.3mg/L, thereby improves the threshold that this series products enters European Union market greatly.Therefore, the inorganic replacement pigment of development of new, extremely urgent.At present, the alternative research and development that contain cadmium pigment have caused that various countries extensively pay attention to, and the U.S., European Union, Russia and Japan and other countries have been developed the multiple mineral dye that does not contain cadmium, and it is painted to be used for pottery, glass, rubber and plastic, paint etc.
Because rare earth 4f electron motion and unique subgrade structure thereof make it show abundant spectrum level, are described as the treasure-house of new and high technology material.Because rare earth element kind more (17 kinds altogether), therefore the sulfide of different types of rare earth element can present distinct colors, particularly the color of the rare-earth sulfide of this wide colour system of redness-yellow has lovely luster, brightness is big, the characteristics that tinting strength and hiding power are strong, the what is more important rare-earth sulfide is nontoxic, and its fusing point is all more than 2000 ℃, under the oxidizing atmosphere temperature up to 400 ℃, under reduction and the inert atmosphere temperature up to more than 1500 ℃, so rare-earth sulfide has the ideal thermal stability.Therefore, the pigment based on the rare-earth sulfide system is considered to one of best non-toxic pigment that substitutes poisonous pigment such as cadmium yellow and cadmium red.Recent years, very active to the research of rare-earth sulfide tinting material and application thereof in the world, be one of the research focus in rare earth material and chemical research field.In the world, countries such as France, Russia, Germany, Japan and the U.S. successively study success and have applied for relevant patent and the Europe and the world patent of country separately.
About the pigment and the application thereof of red lanthanide cerium sulphide system, French Rhodia Inc has successively applied for multinomial patent in China.For example they are at Chinese patents CN 1201441A, and CN1271332A has mainly reported the preparation method of preparation rare-earth sulfide among CN 1426376A and the CN 1087273C, and the improvement of chemical stability and as the purposes of pigment.These rare-earth sulfides mainly can be divided into two classes from structure and chemical constitution: a class is a β type structure, and the chemical structure skeleton symbol can be expressed as Ce
10S
14O
xS
1-x, 0＜x≤1 wherein, oxygen level is at most 0.8%.Another kind of is γ type structure, and the chemical structure skeleton symbol can be expressed as ABS
2, wherein A is at least a kind of basic metal, and B is at least a kind of rare earth metal, and the common general formula of concrete example is KCe
1-xLa
xS
2Or K
xNa
1-xCeS
2(0≤x≤1), alkali-metal content mostly is 50% (molar content) most, and the latter's color gamut is from KCeS
2Color to NaCeS
2Color.In example, the preparation method of the sulfide that these are a series of utilizes cerium raw material (subcarbonate, carbonate or oxide compound) and hydrogen sulfide or/and the mixture of dithiocarbonic anhydride reacts under 600～1000 ℃ temperature, and wherein the volume ratio of dithiocarbonic anhydride and hydrogen sulfide is no more than 0.14 in the sulfiding gas mixture.In order to strengthen the chemical stability of these rare earth sulfide pigments, they utilize chemical processes such as hydrolysis, acid attack and neutralization to coat layer of transparent oxide compound (silicon oxide, titanium oxide, zinc oxide etc.) at its particle surface.Then, prescription and related process have mainly been studied again as the coloring plastic purposes.The work of summarizing them is based on mainly that red cerium sulphide pigment carries out, and reduces synthesis temperature and changes color and luster by adding certain basic metal.
The Merck Patent GmbH of Germany has reported sulfide and the oxysulphide pigments based on flake substrate in Chinese patents CN 111160422C, be characterised in that at flaky mica sheet, SiO
2, TiO
2Or Al
2O
3Deng applying M on the flake substrate
2S
3Yttrium and/or the sulfide of one or more rare earth metals, or corresponding formula M
2S
3-xO
xOxysulfide, wherein M is at least a element that is selected from group of the lanthanides (cerium, neodymium, spectrum, samarium, gadolinium terbium, dysprosium, erbium and thulium) and yttrium, 0.05＜x＜2.5.The preparation method is the salts solution with rare earth metal, joins in the aq suspension of flake substrate, adds alkali then the pH value of this suspension is held constant in the scope that hydrolysis can take place added salt substantially; Then with the presoma that obtains 400～900 ℃ of calcinings, last, at sulfur compound, CS
2, sulphur or H
2S exists down, is translated into sulfide or oxysulfide in 550～1200 ℃, the objective of the invention is to prepare the pigment with pearly-lustre performance.
Reported the preparation method who is equipped with the semicure cerium that a kind of red pigment that contains alkali metal is used among the Chinese patent CN 1111509C, with raw material CeO
2Be placed on the high-temperature zone of Reaktionsofen with additive basic metal carbonate or alkali metal sulfite mixing, sulphur placed cold zone, feed argon gas, switch to hydrogen again, 1100～1500 ℃ down calcining obtain γ type sesquialter cerium sulphide red pigment.
In addition, Japanese patent laid-open 8-259229 and 2619819 has reported respectively with rare-earth chlorination cerium, Sedemesis and has prepared the cerium sulphide red pigment that what obtain respectively is β type and γ type structure.
Above patent can be known, what really embody in invention preparation method mainly is rare earth cerium sulphide system, and other is extra alkali doped element more therein just, and the system color that obtains pigment is red.Though some difference on preparation method's details, but principle is the same basically, utilize high temperature vulcanized reaction to prepare rare earth sulfide pigment exactly, the temperature height is different, the structure difference of the pigment products of preparation, be two classes: β type (tetragonal system) and γ type structure (isometric system), perhaps product is the mixture of two kinds of structures.Total says that color concentrates on red colour system, and color and luster is relatively more dull, so also can limit the application widely of this class pigment.
Summary of the invention
The purpose of this invention is to provide and mix tin (IV) lanthanum sulfide pigment and preparation method thereof.The chemical formula of mixing tin (IV) lanthanum sulfide pigment is: Sn
xLa
2-xS
3+x/2, wherein x is 0≤x≤0.5, its color can carry out the transition to orange and red from yellow gradually.
The present invention utilizes the high temperature solid state reaction principle, feeding rare gas element makes to be reflected under 400～1000 ℃ of nonoxidizing atmosphere and the temperature and carries out, feed sulphur source gas simultaneously, tin (IV) is doped in the lanthanum sulfide matrix, obtains the rare earth sulfide pigment of different colours by the doping of regulating tin.
The preparation method who mixes tin (IV) lanthanum sulfide pigment of the present invention, step and condition are:
Mole metering according to the chemical formula of mixing tin (IV) lanthanum sulfide pigment recently takes by weighing various raw materials, and with the raw material mixing and stirring, put into the reaction boat then, raw material is put in the tube furnace confined reaction stove, feed rare gas element, gas flow is at 0.05～5 liter/minute, and Reaktionsofen is warmed up to 400～800 ℃ then, and temperature rise rate is 5～20 ℃/minute, feed sulphur source gas and rare gas element this moment, and described sulphur source is hydrogen sulfide (H
2S), dithiocarbonic anhydride (CS
2) or the mixed gas of two kinds of gases; Perhaps, with ammonium thiocyanate (NH
4SCN) mixed gas of heating and melting decomposition generation is as the sulphur source, and this mixed gas contains H
2S, CS
2, NH
3, S and HSCN, at 400～800 ℃ of insulation 2h, described rare gas element, continue to be warmed up to 900～1200 ℃ then, temperature rise rate is 5～20 ℃/minute, at this temperature range insulation 2h, stops heating then, stop to lead to, logical sulphur source gas and rare gas element naturally cool to room temperature, stop logical rare gas element, reaction product is ground evenly, obtain mixing tin (IV) lanthanum sulfide pigment.
Described raw material is:
Metallic tin is tindioxide (SnO
2), its purity 〉=98%, described purity is the tin mass percent of the content of other metal relatively.；
Rare Earth Lanthanum adopts oxide compound, and the salt of various ways is halogenide, carbonate, subcarbonate, oxalate, vitriol or nitrate; Consider the product situation of economic element and rare earths material, preferred rare earth oxide or rare earth carbonate, the purity of lanthanum element 〉=99% wherein, described purity is the lanthanum mass percent of the content of other metal relatively.
Used sulphur source can have two kinds: in first kind of technical scheme, available sulphur source is bottled hydrogen sulfide (H
2S), dithiocarbonic anhydride (CS
2) or the mixed gas of two kinds of gases; Control their flow by the gas dosing meter.In second kind of technical scheme, utilize ammonium thiocyanate (NH
4SCN) (purity: technical pure, 〉=98%) is decomposed the mixed gas that produces at 150～250 ℃ of following heating and meltings and is used as the sulphur source, and this mixed gas contains H
2S, CS
2, NH
3, S and HSCN.
Rare gas element is with bottled high-purity argon gas (purity 〉=99.99%) or high pure nitrogen (purity 〉=99.99%).Above-mentioned bottled gas is before feeding the high-temperature tubular Reaktionsofen, and the cleaner that all needs the affiliated professional and technical personnel in this area to use always is taken off the moisture content in the gas, because moisture content can produce certain influence to building-up reactions.
For remaining sulphur source gas such as H in the reaction process
2S, CS
2Deng, directly connect feeding copper sulfate (CuSO with rubber hose
4), zinc sulfate (ZnSO
4) saturated aqueous solution absorb, can generate by product cupric sulfide (CuS) and zinc sulphide (ZnS) like this, occur with sedimentary form, filter oven dry then.These two kinds of materials are good semiconductor materials, in work is produced, can be used as industry byproduct and sell.The concentration of the above-mentioned aqueous solution is variable, and the saturation concentration under can be from zero-dose to envrionment temperature of living in is considered preferred saturated solution from economic angle.And raw material CuSO
4And ZnSO
4Purity, select different purity according to the purposes needs of by product.Also can use basic metal (Li, Na in addition, the saturated aqueous solution of oxyhydroxide K), muriate, carbonate, nitrate and vitriol absorbs, same as above, directly connect to feed in the aqueous solution with rubber hose and get final product, preferred the sort of starting material mainly consider from economic angle, do not influence and have for preparation feedback itself, the concentration of the above-mentioned aqueous solution is variable, saturation concentration under can be from zero-dose to envrionment temperature of living in is considered from economic angle, preferred saturated solution.The alkali-metal sulfide of by product that generates can be as the raw material of producing the pigment of mixing alkali-metal rare-earth sulfide.The purity of these alkali-metal raw materials gets final product more than reaching technical pure.
Therefore whole process of preparation mainly is divided into two stages: the fs is 500～700 ℃, and this stage is SnS
2The beginning generation phase, if make raw material with the carbonate of Rare Earth Lanthanum, at this temperature section, carbonate can decompose the generation oxide compound gradually, raises SnS then with temperature
2Fusion gradually, and as the oxide compound of fusing assistant and lanthanum reaction generates sulphur lanthanum trioxide compound.Subordinate phase is 800～1000 ℃, is that the sulphur lanthanum trioxide of mixing tin is converted into the lanthanum sulfide stage in this temperature range.On structure, in two phase process, the γ type structure of the structure of rare earth lanthanum sulfide system from the β type structural transformation of tetragonal system to isometric system with respect to the former, has the back and plants the rare earth sulfide pigment of structure and have higher thermal stability.
Rare earth lanthanum sulfide (La
2S
3) have γ type structure, belong to isometric system Th
3P
4Generally there is cationic hole in crystalline phase in its structure, so Sn (IV) ion can be incorporated in these positively charged ion holes until saturated, in addition SnS
2Itself also presents certain color, is generally golden yellow.So, Sn
4+Ion can be with different ratios (with La
3+The ionic mol ratio) is doped to La
2S
3In the system, when selecting different doping ratios, the corresponding electronic structure and the shade of color of whole product system will change.The chemical molecular skeleton symbol of whole pigments system is expressed as Sn
xLa
2-xS
(3+x/2), wherein when the doping volumetric molar concentration x of tin (IV) when 0 carries out the transition to 0.5, the color of its pigments system, meeting is along with the increase gradually of the doping of tin (IV), deepen gradually from faint yellow, to redness and scarlet, integral body is the trend that deepens gradually to safran, orange.And the sign of the structure of whole system by X ray powder diffracting technology shows its isometric system Th
3P
4The structure of crystalline phase is kept, and is the difference because of the doping of tin (IV), and unit cell parameters presents small variation.
The structure of prepared series characterizes with X ray powder diffracting technology, and correspondingly with standard JCPDS card determines structure type.Used instrument is Rigaku-D/max 2500 V x-ray diffractometers, test condition: temperature, 298 K; The Cu target, λ=1.54178 , 40KV, 200mA; The scanning angle scope, 10～90 °.Analytical results is seen accompanying drawing 1.Corresponding with standard card, the result shows that the structure of products therefrom is an isometric system, Th
3P
4Crystalline phase, γ type structure.
The chromaticity coordinates of product provides trichromatic coefficient L with the CIE1976 system
*, a
*And b
*, define by Commission International d ' Eclairage (International Commission on Illumination).Concrete grammar is to test solid diffuse reflectance spectra (seeing accompanying drawing 2) by Hitach Uv-4100 spectrophotometer earlier, utilizes software to calculate the chromaticity coordinates value of corresponding product then.Test result and outward appearance show, the technology of the present invention is prepared, and to mix tin rare earth lanthanum sulfide pigment nontoxic, thermal stability is good, bright in colour, advantages such as the big and dispersion force of colour brightness is good, can be widely used in many industrial circles painted especially for material of construction such as plastics, paint, coating, rubber, leather, pottery, printing ink, paper, makeup and cement.
The present invention can be used as the yellow extremely preparation method's who mixes tin (IV) lanthanum sulfide of red colour system pigment advantage:
1. utilize doped metallic elements tin, but and what the method for content that changes tin can obtain yellow easily to red series and color continually varying rare earth sulfide pigment.Therefore, just can obtain the pigment of multicolour (yellow-to red) based on a kind of rare-earth sulfide matrix, and lanthanum is that content is abundant and comparatively cheap a kind of in the rare earth element, therefore raw material will have lower cost and considerable application prospect like this.
2. because the sulfide of adulterated tin (IV) element has lower fusing point, therefore can reduce the synthesis temperature of whole pigments system product, have energy-saving advantages.
3. a kind of technical scheme in the sulphur source of the present invention's employing is to utilize the method for ammonium thiocyanate heating and melting to obtain sulphur source gas, this method is owing to hydrogen sulfide containing content in the mixed gas is lower, so security is higher, and ammonium thiocyanate is cheap, be solid-state, transportation and storage are convenient, have reduced production cost.
4. the treatment process of residue sulphur provided by the invention source gas is based on the angle of recycling and sets out, rather than usually residual gas directly is discharged into atmosphere and incendiary method, the method applied in the present invention, not only absorbed the reaction residual gas effectively, and can obtain the by product of economic worth, this method safety, environmental protection and energy-conservation have reduced production cost.
Description of drawings
Accompanying drawing 1 is the powder x-ray diffraction spectrogram of the rare earth lanthanum sulfide pigment of the serial doped tin (IV) of correspondence among the embodiment, and X-coordinate is a diffraction angle, and ordinate zou is a diffracted intensity.
Accompanying drawing 2 is solid diffuse-reflectance spectrograms of the rare earth lanthanum sulfide pigment of the serial doped tin (IV) of correspondence among the embodiment, and X-coordinate is a wavelength, and ordinate zou is a reflectivity.
Embodiment:
Chemical structural formula by product is Sn
0.005La
1.995S
3.0025In the molar content of various raw metals and raw material total amount be that 500 grams take by weighing raw material tindioxide (purity 〉=98%) and rare earth lanthanum oxide (purity 〉=99%), with they mixing and stirring, put into then and react boat, put into tube furnace again.Then, the confined reaction stove feeds high-purity argon gas (purity 〉=99.99%), and gas flow feeds the ammonium thiocyanate heating and melting and produces sulphur source gas at 0.1 liter/minute after 10 minutes.Be 10 ℃/minute by temperature rise rate then, the high-temperature tubular Reaktionsofen be warmed up to 700 ℃, under this temperature, be incubated 4h.Continue logical sulphur source gas and rare gas element, continue to be warmed up to 900 ℃ then, temperature rise rate is 10 ℃/minute, is incubated 1h under this temperature, stops heating and logical sulphur source gas then, and naturally cooling continues logical rare gas element.Temperature drops to 150 ℃, stops logical rare gas element, and product is ground evenly, and obtaining chemical structural formula is Sn
0.005La
1.995S
3.0035Yellow product, the CIE chromaticity coordinates is: L
*=77.270, a
*=6.514, b
*=43.699.
Feed copper sulfate (CuSO successively for tail gas in the reaction process (remaining unreacted sulphur source gas)
4, purity 〉=98%) and zinc sulfate (ZnSO
4) saturated aqueous solution of (their purity 〉=98%) absorbs for 10 liters, generates by product cupric sulfide (CuS) and zinc sulphide (ZnS) like this, occurs with sedimentary form, filters then, oven dry is ground and is evenly obtained byproduct.
Ammonium thiocyanate heating and melting recited above produces the method for sulphur source gas
Raw material ammonium thiocyanate NH
4SCN (technical pure, purity 〉=98%) once adds 700g and goes in the Glass tubing of vertical tube type resistance furnace (2KW, 30～400 ℃ of Heating temperatures), airtight then, link to each other with high temperature process furnances with rubber hose, be warmed up to 180 ℃, keep this temperature-resistant, obtain sulphur source gas.
Embodiment 2
Rare earths material adopts Phosbloc, and other is with embodiment 1.Obtain yellow product, the CIE chromaticity coordinates is: L
*=77.270, a
*=6.514, b
*=43.699.
Embodiment 3
H is adopted in the sulphur source
2S, 0.05 liter/minute of gas flow, other obtains yellow product with embodiment 1, and the CIE chromaticity coordinates is: L
*=77.270, a
*=6.514, b
*=43.699.
Embodiment 4
By chemical structural formula is Sn
0.05La
1.95S
3.025In the molar content of various raw metals and raw material total amount be that 500 grams take by weighing raw material tindioxide (purity 〉=98%) and rare earth lanthanum oxide (purity 〉=99%), other obtains the safran product with embodiment 1, the CIE chromaticity coordinates is: L
*=68.905, a
*=23.918, b
*=37.914.
Embodiment 5
CS is adopted in the sulphur source
2, 0.05 liter/minute of gas flow; High-purity gas adopts high pure nitrogen (purity 〉=99.99%), and other obtains the safran product with embodiment 4, and the CIE chromaticity coordinates is: L
*=68.905, a
*=23.918, b
*=37.914.
Embodiment 6
The raw material of rare earth lanthanum adopts Phosbloc, and other are with embodiment 4,0.05 liter/minute of gas flow
2, other obtains the safran product with embodiment 1, and the CIE chromaticity coordinates is: L
*=68.905, a
*=23.918, b
*=37.914.
Embodiment 7
Press chemical structural formula Sn
0.4La
1.6S
3.2In the molar content of various raw metals and raw material total amount be that 500 grams take by weighing raw material tindioxide (purity 〉=98%) and rare earth lanthanum oxide (purity 〉=99%), other obtains red product with embodiment 1, the CIE chromaticity coordinates is: L
*=50.558, a
*=23.050, b
*=13.670.
Embodiment 8
H is adopted in the sulphur source
2S and CS
2, volume ratio 3: 2, total flux are at 0.05 liter/minute, and other obtains red product with embodiment 7, and the CIE chromaticity coordinates is: L
*=50.558, a
*=23.050, b
*=13.670.
Embodiment 9
The raw material of rare earth lanthanum adopts Phosbloc, and other obtains red product with embodiment 7, and the CIE chromaticity coordinates is: L
*=50.558, a
*=23.050, b
*=13.670.
Claims (7)
1. mix tin (IV) lanthanum sulfide pigment, it is characterized in that chemical formula is: Sn
xLa
2-xS
3+x/2, wherein x is 0≤x≤0.5.
2. tin (IV) the lanthanum sulfide method for preparing pigment of mixing as claimed in claim 1 is characterized in that step and condition are:
Mole metering according to the chemical formula of mixing tin (IV) lanthanum sulfide pigment recently takes by weighing various raw materials, and with the raw material mixing and stirring, put into the reaction boat then, raw material is put in the tube furnace, the confined reaction stove, feed rare gas element, gas flow is at 0.05～5 liter/minute, and Reaktionsofen is warmed up to 400～800 ℃ then, and temperature rise rate is 5～20 ℃/minute, feed sulphur source gas and rare gas element this moment, at 400～800 ℃ of insulation 2h, continue to be warmed up to 900～1200 ℃ then, temperature rise rate is 5～20 ℃/minute, at this temperature range insulation 2h, stop heating then, stop logical sulphur source gas and rare gas element, naturally cool to room temperature, reaction product is ground evenly, obtain mixing tin (IV) lanthanum sulfide pigment;
Described raw material is:
Metallic tin is a tindioxide, its purity 〉=98%, and described purity is the mass percent of tin with respect to other impurity;
Rare Earth Lanthanum adopts oxide compound, and the salt of various ways is halogenide, carbonate, subcarbonate, oxalate, vitriol or nitrate;
Used sulphur source is the mixed gas of hydrogen sulfide, dithiocarbonic anhydride or two kinds of gases; Perhaps, use ammonium thiocyanate, its purity is technical pure, decomposes the mixed gas that produces at 150～250 ℃ of following heating and meltings and is used as the sulphur source, and this mixed gas contains H
2S, CS
2, NH
3, S and HSCN;
The rare gas element high-purity argon gas, its purity 〉=99.99%; Or high pure nitrogen, its purity 〉=99.99% all will be taken off the moisture content in the gas.
3. tin (IV) the lanthanum sulfide method for preparing pigment of mixing as claimed in claim 2, it is characterized in that, the raw material of described Rare Earth Lanthanum adopts rare earth oxide or rare earth carbonate, the purity of lanthanum element 〉=99% wherein, and the purity of described lanthanum element is the lanthanum element content of other metallic element relatively.
4. tin (IV) the lanthanum sulfide method for preparing pigment of mixing as claimed in claim 2, it is characterized in that, the saturated aqueous solution of one or more in the vitriol of waste gas utilization copper, zinc and the nitrate muriate absorbs, cupric sulfide and zinc sulphide, occur with sedimentary form, filter then, oven dry, grind evenly, obtain by product cupric sulfide and zinc sulphide.
5. tin (IV) the lanthanum sulfide method for preparing pigment of mixing as claimed in claim 2, it is characterized in that, tail gas absorbs with the saturated aqueous solution of alkali-metal oxyhydroxide, muriate, carbonate, nitrate or vitriol, described basic metal is Li, Na or K, and obtaining by product is alkali-metal oxyhydroxide, muriate, carbonate, nitrate or vitriol.
According to claim 4 mix tin (IV) lanthanum sulfide method for preparing pigment, it is characterized in that the vitriol of copper, zinc, nitrate and muriatic purity is greater than 98%, its purity is copper or the zinc mass percent with respect to other impurity.
7. mix tin (IV) lanthanum sulfide method for preparing pigment according to claim 2, it is characterized in that, the raw material of described Rare Earth Lanthanum element is to choose any one kind of them in lanthanum trioxide, Phosbloc, Lanthanum trichloride, lanthanum sulfat and the lanthanum nitrate, and described lanthanum is 〉=99% with respect to the mass percent of other impurity.
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| CN102390856A (en) * | 2011-11-14 | 2012-03-28 | 西北工业大学 | Method for preparing high-stability gamma-phase nanometer lanthanum sulfide powder in low temperature |
| JP2013159554A (en) * | 2012-02-07 | 2013-08-19 | Muroran Institute Of Technology | Method of growing crystal of rare earth sesquisulfide |
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| CN102390856A (en) * | 2011-11-14 | 2012-03-28 | 西北工业大学 | Method for preparing high-stability gamma-phase nanometer lanthanum sulfide powder in low temperature |
| JP2013159554A (en) * | 2012-02-07 | 2013-08-19 | Muroran Institute Of Technology | Method of growing crystal of rare earth sesquisulfide |
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